Catalytic and Electrochemical Release of Solar Energy Stored in Strained Organic Compounds

存储在应变有机化合物中的太阳能的催化和电化学释放

• 批准号: 392607742
• 负责人: Professor Dr. Julien Bachmann, Ph.D.
• 金额: --
• 依托单位: Institut für Chemie und Biochemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2018
• 资助国家: 德国
• 起止时间: 2017-12-31 至 2022-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/392607742?language=en
• 关键词: Catalytic; Electrochemical; Release; Solar; Energy

We envision that solar energy conversion and storage could be integrated via intramolecular reactions in single molecule systems. Such processes would combine key features of photovoltaic and photochemical methods in the most simple and efficient manner. The prototypical example for such an intramolecular reaction is the photochemical conversion of norbornadiene (NBD) to its metastable valence isomer quadricyclane (QC), a single-photon, single-molecule process in which bond-breaking and bond-making events are simplified to the maximum. The reverse reaction from QC to NBD releases up to 100 kJ/mol, making QC a solar fuel with an energy density comparable to state-of-the-art batteries.This project aims at generating the fundamental knowledge to unleash the full potential of chemical energy storage in strained organic molecules. Three major challenges associated with the energy release reaction will be addressed: (1) Its catalytic triggering: Starting from a fundamental understanding of the catalytically triggered cycloreversion and its undesired side-reactions, such as dehydrogenation and C-C bond scission, we will aim at developing catalysts with enhanced selectivity and higher reversibility in the storage cycle. (2) Its electrochemical triggering: Based on a fundamental understanding of the electrochemically triggered cycloreversion, we will aim at improving the reversibility of the storage cycle by design of electrodes and electrochemical environments which limit undesired side-reactions and electrode fouling. (3) The direct conversion to electrical energy: As a grand challenge we envision an "energy-storing solar cell", i.e. the direct conversion of the chemical energy stored in QC to electrical energy. To this aim, we will design hybrid interfaces with appropriate electronic structure, chemical structure and electrochemical stability to demonstrate the feasibility of this new concept.To tackle these very ambitious goals, the groups of Bachmann, Libuda, and Papp have teamed up to combine their complementary expertise in surface science, in-situ spectroscopy, electrochemistry, and materials science. The project team will study the mechanism, kinetics, energetics and stability of the NBD/QC system and its derivatives in ultrahigh vacuum, at ambient pressure, at solid/liquid interfaces and under (photo)electrochemical conditions. Combining aspects of insight gained from single crystal studies, complex model catalysts, and nanostructured materials, we will obtain a detailed understanding of the energy release reaction and the factors that currently limit its reversibility. We will then use this knowledge to develop improved catalytic and electrochemical storage systems, i.e. combinations of molecules, materials, and methods enabling "single-photon, single-molecule" energy conversion and storage in a better controlled, more efficient, and more reversible fashion.

我们设想太阳能转换和存储可以通过单分子系统中的分子内反应来集成。这种方法将以最简单和有效的方式结合光电和光化学方法的联合收割机关键特征。这种分子内反应的典型例子是降冰片二烯（NBD）到其亚稳价态异构体四环烷（QC）的光化学转化，这是一个单光子、单分子过程，其中键断裂和键形成事件被简化到最大。从QC到NBD的逆反应释放高达100 kJ/mol的能量，使QC成为能量密度与最先进电池相当的太阳能燃料。该项目旨在产生基础知识，以释放应变有机分子中化学储能的全部潜力。与能量释放反应相关的三个主要挑战将得到解决：（1）其催化触发：从对催化触发的环化反应及其不希望的副反应（如脱氢和C-C键断裂）的基本理解开始，我们将致力于开发在存储循环中具有增强的选择性和更高可逆性的催化剂。(2)其电化学触发：基于对电化学引发的循环逆转的基本理解，我们将旨在通过设计电极和电化学环境来限制不期望的副反应和电极结垢，从而改善储存循环的可逆性。(3)直接转换为电能：作为一个巨大的挑战，我们设想一种“储能太阳能电池”，即将QC中储存的化学能直接转换为电能。为了实现这一宏伟目标，Bachmann、LiNbO_3和Papp三个研究小组联合收割机将他们在表面科学、原位光谱学、电化学和材料科学领域的互补专长结合起来，并将其应用于纳米材料的制备。项目团队将研究NBD/QC系统及其衍生物在真空、环境压力、固/液界面和（光）电化学条件下的机制、动力学、能量学和稳定性。结合从单晶研究，复杂模型催化剂和纳米结构材料中获得的见解，我们将详细了解能量释放反应和目前限制其可逆性的因素。然后，我们将利用这些知识来开发改进的催化和电化学存储系统，即分子，材料和方法的组合，使“单光子，单分子”能量转换和存储在一个更好的控制，更有效，更可逆的方式。